Alkylation



Feb. 12, 1946.

R. A. KINNEAR ET AL y ALKYLATION Filed Jan. 28, 1942 `INVENTORS TI'ORNEY Patented Feb. 12, 1946` ica Jack F. McCanne,

C. Gordon, Beaumont,

- sony-Vacuum New York. N. Y.,

glnald A. Kinnear, Harold B. chamberiain. George T. Fail, and John (lilL Company. Incorporated. a corporation of New York Application January zs, 1942, ssi-uu no. 493.446 a cnam. (ci. aso-esas) This invention relates to process and apparatus for alkylation of iso-paraiiins with olefins in the presence of a fluid acid catalyst and is particularly concerned with process steps for preparation and mixing of .the reaction mass in such reactions as well as apparatus adaptedto practice of said steps.

'In processes of the present type, an iso-parafthe reactor in such nn and an olefin, for example, iso-butane and'- I butylene, are reacted in the presence ofl a fluid acid catalyst such as sulphuric acid, hydrofiuoric acid and the like, to produce high anti-knock hydrocarbons within the gasoline boiling range.

The iso-paraffin is normally 4in a mixture of C;

hydrocarbons resulting from refinery operations` or other suitable source, said mixture also containing the y4 carbon atom olens with which the iso-butane is to be alkylated. This mixture, suitably. enriched with additional iso-paraiiln to maintain the desired ratio of reactants, is mixed with the acid catalyst and passed to a reactor. In a strict sense, the entire system containing reactants and catalyst constitutes the reaction zone but in this specification and in the appended claims the term reaction zone will be used to designate the region wherein a reaction mass is maintained, i. e., the reactor. From the reactor two streams are withdrawn, usually in continuous manner. One of the withdrawn streams is passed to a settling drum wherein the acid catalyst separates from an oily layer consisting of alkylated, unreacted hydrocarbons and the like.. The separated acid is returned in part to the reaction mass and the remainder is withdrawn from the system as spent catalyst. The oily layer is treated to remove the desired product and separate alight fraction containing the isofparafiln which is then recirculated for'admixture with fresh feed. Aportion of the crude product mixture containing unreacted iso-parafin molar excess, as is the normal practice. The external circuit is also of importsnce'in maincontact of reactants with catalyst. A mixing device in the external circuit itself causes .establishment of an emulsion of reis introduced to Y vmanner as stant agitation of the large body of fluids therein. Auxiliary means may also be provided for this purpose auch as "s tirrers and/or bottom eductor as described' in the copending application of Julius B. Middleton, Serial No. 422,381 filed December 10, v1941. The external circuit is also utilized as admeans of controlling the reaction temperature. Cooling coils are provided in this circuit Ito augment the effect of direct temperature control applied to ensure that'such reaction as occurs inthe external emulsion circuit shall not upset conditions in the reactor by overheating of the stream to the reactor. v

In spite of careful control by means o! the expedients discussed above, there still remain problems of operation, important among Vwhich are features connected with introduction of materials to and control action is, of course, initiated as soon as Areactants and catalyst are .brought into contact. Improper control at this point'mayl result in extremely reduced yields of excessively low quality. We have developed a process and apparatus lending itself to ready and accurate control as regards rapid compensation for variations in operating conditions as well der relatively'constant conditions.

-n is sometimes returned to the reaction mass l as such without fractionation.

The second stream withdrawn from the reac- 1 tor is used in establishing and maintaining a circuit of reaction mass external to the reactor. -Fresh hydrocarbon feed ,and fresh acid catalyst are added to this external circuit of hydrocarbonacid emulsion which is made to serve .several important purposes. It is essential that a high ratio of paraffins to oleiins be maintained in order to minimize polymerization of the olenns. Recirculation of the reaction mass to and from a' large body of reaction mixture in the reactor result in building up a large excess of tertiary paraiilns in'the system when these are'fed to the reaction Essentialiy,-the invention contemplates' a plurality of mixing devices in series in the external emulsion circuit.- Means are preferably provided 'for supplying bothrecycled reaction mass admixed with fresh catalyst and fresh feed stock admixed with recycled hydrocarbons to the mixing stream in portions in advance .ofeach of the mixers. .Additional improvement in operation is achieved by using, as a substantial proportion .product separated lfrom 'acid catalyst and supf in the total hydrocarbon feed as supplied to the external circuit.

The nature of the from ofinideration of a specific form thereof ilfresh and recycled acid.

t0 Provide conthe reactor and to of the external circuit. Re-

as stable operation-uninvention and additional objects and advantages thereof will be apparentv withdrawn and split into a stream rejected from the system through line 'I as spent catalyst and astream returned to the reactor through 1ine.8.

The hydrocarbon stream passed through line 8 constitutes crude product, at least a portion of which is transferred through line 9 to a distillation system 4wherein it is fractionated to obtain the desired alkylate free of unreacted C4 hydrocarbons. The latter are closely fraction ated to recover the iso-butano portion thereof which is returned to the process by way of pipe I0.l

A second stream passes from the reactor by way of line II and is joined by a stream of fresh acid catalyst from line I2, after which the mixture is propelled by pump I3 to a manifold I4 for supply to devices for. mixing it with hydrocarbons to be supplied to the reactor. The said hydrocarbons are a mixture prepared prior. to.

contact with the emulsion from pipe I3 by addingiso-butane recycled from the distillation operation to the fresh C4 feed stock comprising isobutane and butylenes from line I5. Preferably these hydrocarbons are further augmented by the acid in drum 4 and supplied for that purpose through line I B. The mixture ofhydrocarbons is passed through a mixing'device I1 and supplied to a manifold I8.

An important aspect of the invention is a preferred composition of the mixture in manifold I8. Whereas the art has normally employed isoparafiin to oleiln ratios on the order of 3 or 4 to 1; we have found that marked improvement is obtained by so proportioning the supply of reactants from the several sources thereof as to 1. 'I'he hydrocarbon feed as flrst brought into contact with the acid catalyst therefore contains at least and not more than 30 parts of isoparaffin for each part of olefin by weight.

The emulsion from manifold I4 and the hydrocarbons from manifold I8 are thoroughly admixed with each othery in a plurality of mixing devices 20 in series, which devices may be of any suitable designsuch as bailled chambers, orifice mixers, nozzles and-the like. From the mixers 2U, the emulsion is returned to thev reactor through line 2|. A very efllcient mixer suitable for the purpose is described in application Serial No. 422,362, filed December l0, 1941, by Julius B. Middleton. Although good results are obtained by joining the complete streams from the two manifolds and passing the mixture through the series of mixers 2U, we prefer to split the feed from at least one and preferably both of the manifolds and supply the fiuidstherefrom tothe external circuit in portions; each portion being delivered to the `mixing line in advance of'a mix- 4ing device 20.

The mixers are suitably cooled, as by heat exchange coils in the usual manner and the' concept of split feed aids greatlyln maintaining y adequate cooling eect as well as greatly smoothcuit. In both cases, of course, the load on the distillation system is reduced materially while maintaining desired conditions of concentration ratios within the system.

As shown in the drawing, the branch pipes supplying fluids from manifolds I4 and IB to series of mixers 20 are equipped with valves I9. Depending on operating conditions, the flow of either or both fluids to the entry of any mixer 20 may be modified. If desired, the entire flow of either or both manifolds may be routed to the first mixer in the series at the discretion of the operator. This flexibility of mixing control coupled with the large heat exchange capacity acting on fluids in turbulent flow is an important aspect of the invention. Anotheradvantageous feature is the extensive contact between the mixeclfluids provided by the present invention.

l. The process which comprises maintaining in a reaction zone a reaction mass resulting from addition thereto of hydrocarbons separated from Y. l

v fresh catalyst to said second stream to form a recycle mixture, admixing fresh feed stock conmaintain a ratio of between about 15 and30 to the alkylation of tertiary parafllns with olefins in the presence of a fluid acid catalyst, withdrawing a first stream from said mass, settling said f'lrst stream in a settling zone to-separate a crude product from catalyst, separating unreacted tertiary parafilns from' a portion of said crude prodf uct, passing a second portion of said crude product for return to the reaction zone, withdrawing a second stream from said reaction mass, adding taining olefins and tertiary paraffins with said second portionof said crude product and with said separated tertiary paraffin to form a hydrocarbon feed mixture, separating each of said mixtures into a plurality of portions, mixing one portion of each of said mixtures with each other to form a reaction mixture, passing said reaction mixture through a plurality of agitating zones in series, agitating said reaction mixture in each of said agitating zones, adding an additional portion of each of said recycle mixture and said feed mixture between each pair of successive agitating zones, and passing the so agitated reaction mixture to said reaction zone.

l yto the, reaction-zone, withdrawing a second stream from said reaction mass, adding fresh catalyst to said second stream to form a recycle mixture, admixing fresh feed stock containing oleilns and tertiary parafllns with said second portion of said crude product and with said separated tertiary parafln to. form a hydrocarbon feed mixture, separating one of said mixtures into a plurality of portions, mixing one portion of said mixture so separated with at least a partof the other of said mixtures to form a reaction mixture, passing said reaction mixture through a plurality of agitating zones in series, agitating ling a stream from said mass,

said reaction mixture in each of said agitating zones, adding an additional portion of said separated mixture between each pair of successive agitating lzones, and passing the so agitated reaction mixture to said reaction zone.

ing tertiary parafilns and olens, separating each of said mixtures into a plurality of portions, mixing one portion of each of said mixtures with each other to form a reaction mixture, passing said reaction mixture through a plurality of agitating zones in series, agitating said reaction mixlture in each. of said agitating zones; adding an additional portion of e'ach of said recycle mixture and said feed mixture between each pair of successive agitating zones, and passing the so agitated reaction mixture to said reaction zone.

4. The process which comprises maintaining in a reaction zone a reaction mass resulting from the alkylation of tertiary paraiilns with olens in the presence of a fluid acid catalyst, withdrawing astream fromsaid mass, adding fresh catalyst to said stream to form a recycle mixture,

providing a hydrocarbon feed mixture, containing tertiary paraiflns and olens, separating one of said mixtures into a plurality of portions, mixing one portion of said mixture so separated with at least a partof the otheriof said mixtures to form a reaction mixture, passing said reaction mixture through a plurality of agitating zones in series, agitating said reaction mixture in each of said agitating zones, adding-an additional portion of said separated mixture between eachpair of successive agitating zones, and passing the so agitated reaction mixture to said reaction zone.'

5. The process which comprises maintaining in a reaction zone a reaction mass resulting from the alkylation of isdbutane with butylene'in the presence of a fluid acid catalyst, withdrawing a nrst stream from said mass, settling said first stream in a settling zoneto separate a crude product from catalyst, separating unreacted isobutane from a portion of said crude product, passing a second'portion of said crude product for return to the reaction zone, withdrawing a second stream from said'reactionmass, adding fresh catalyst to said second stream to form a recycle mixture, admixingfresh feed Qstock containing butylene and tertiary 'paramns with .said second portion of said Vcrude product and with, said separated iso-butane to form a hydrocarbon feed mixture, separating each of said mixtures into a plurality of portions, mixing one portion of each of said mixtures with each other to form a reaction mixture, passing said reaction mixture through a plurality of agitating zones inV series, agitating said reaction mixture in each of said agitating zones, adding an additional portion'of each of said recycle mixtures and said feed mixpresence of a fluid acid said stream to form lyst, separating unreacted iso-brutane from a portion of said crude product, passing a secondportion of said crude product for return to the reaction zone, withdrawing a second stream from said reaction mass, adding fresh catalyst to said second stream to forma recycle mixture, admixg ing fresh feed stock containing butylene and isobutane with said second portion of said crude product4 and with said separated isobutane to form a hydrocarbon feed mixture, separatingv of said agitating zones, adding an additional portion of said separated mixture between each pair ofsuccessive agitating zones, and passing the so agitated reaction mixture to said reaction zone.

'7. The process which comprises maintaining in a reaction zone a reaction mass resulting from the alkylation of isobutane with Ebutylene in the presence of a fluid acid catalyst, withdrawing a stream from said mass, adding fresh catalyst to said stream to' form a recycle mixture, providing a hydrocarbon feed mixture, containing isobutane and butylene, separating each of said mixtures into a plurality of portions, mixing one portion of eachof said mixtures with each other to form a reaction mixture,I passing saidreaction mixture through a plurality of agitating zones in series, agitating .said reaction mixture in each of said agitating zones, adding an additional portion of each of said recycle mixtures and feed -mixturebetween each pair of successive agitating zones, and passing theso agitated reaction mixture to said reaction'zone.

8. The process which comprises maintaining in a reaction zone a reaction mass resulting from the alkylation of isobutane with rbutylene in the catalyst, withdrawing a adding fresh catalyst to a recycle mixture. providing a hydrocarbon feed mixture, containing isobutane 4vand butylene, separating one of said mixtures into a plurality of portions, mixing one portion of said mixture so separated with at least a part of the other of said mixtures to form a reaction mixture, passing said reaction mixture through a plurality of agitating zones ink series, agitating said reaction mixture in each of said stream from said mass,

said separated mixture between each pair of successive agitatingzones, and passing the so agitated reaction mixture to said reaction zone.

9. The process which comprises maintaining in a reaction zone a reaction mass resulting from the alkylation of tertiary paraiiins' with oleiins in the presence of a fluid acid catalyst, withdrawing a first streamfrom said mass, settling said first stream in a settling zone to separate ture between each pair of successive agitating zones, and passing the so agitated reaction mixture to said reaction zone. v

6. The process which comprises maintaining in a reaction zone a reaction massresulting from the alkylation of isobutane with butylene in thev presence'of a fluid acid catalyst,vwithdrawin8 a first stream from said mass, settlingsaid first stream to separate a crude product from a crude product from' catalyst, separating unreacted -tertiary vparaiiins from a portion of said crude product, passingva second portion of said crude product for return to the reaction zone, withdrawing a second stream from said reaction mass, adding fresh catalyst to said second stream to form a recycle mixture; admixing fresh feed stock containing volefins and tertiary paramns with said second portion loi."said orude product and with said separated tertiary paramn to form' mixture, separating each of a hydrocarbon feed said mixtures into ing one portion of a -plurality of portions, mixeach of, said mixtures with adding an additional portion of each other to form a reaction mixture, passing taining at least about 15 and not more thanabout said reaction mixture through a plurality of agi- 30 parts of said tertiary paraflin for each part of tating zones in series, agitating said reaction said olefin fby Weight.

mixture in each of said agitating zones, adding an additional portion of each of said recycle .G REGINALD A. KINNEAR. mixture and said fresh feed mixture between HAROLD B. CHAMBERLAIN. each pair of successive agitating zones, and pass- JACK F. McCANNE.

ing the so agitated reactionmixturev to said re- GEORGE T. FAILS.

action zone, said hydrocarbon feed mixture con- JOHN C. GORDON. 

